EP2377963B1 - Matériau en acier résistant à la corrosion pour pétrolier de brut - Google Patents

Matériau en acier résistant à la corrosion pour pétrolier de brut Download PDF

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Publication number
EP2377963B1
EP2377963B1 EP09835097.8A EP09835097A EP2377963B1 EP 2377963 B1 EP2377963 B1 EP 2377963B1 EP 09835097 A EP09835097 A EP 09835097A EP 2377963 B1 EP2377963 B1 EP 2377963B1
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mass
corrosion
steel
corrosion resistance
crude oil
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German (de)
English (en)
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EP2377963A4 (fr
EP2377963A1 (fr
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Tsutomu Komori
Kazuhiko Shiotani
Yasuto Inohara
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JFE Steel Corp
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JFE Steel Corp
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D

Definitions

  • the present invention relates to corrosion-resistant steel products for crude oil tanker for use in different corrosion environment portions, such as oil tanks or ballast tanks of crude oil tankers.
  • the present invention relates to corrosion-resistant steel products for crude oil tanker capable of suppressing local corrosion occurring in the bottom plate of oil tanks of crude oil tankers and general corrosion occurring in the top board or the side plate thereof and further corrosion occurring in the coated surface of the ballast tanks on the back side of the bottom plate of oil tanks.
  • the H 2 S is oxidized by catalyst action of iron rust generated by corrosion to become a solid S (elemental sulfur) and is present in the form of a layer in the iron rust.
  • Examples of the causes for the bowl-shaped local corrosion include:
  • the most effective method for suppressing the above-described corrosion is subjecting the surface of steel products to heavy coating for protecting the steel products from the corrosion environment.
  • the heavy coating of crude oil tanks need considerable expense for coating or inspection because the coating area becomes large or in the corrosion environment of crude oil tanks, when heavy coating is carried out, corrosion of a damaged coating film portion is promoted on the contrary.
  • Patent Literature 1 discloses corrosion resistant steel for cargo oil tanks excellent in general corrosion resistance or local corrosion resistance in which, to a steel containing C: 0.01 to 0.3 mass%, Si, Mn, P, and S are added in a proper amount, Ni: 0.05 to 3 mass% is further added, and Mo, Cu, Cr, W, Ca, Ti, Nb, V, and B are selectively added.
  • Patent Literature 1 discloses that, in a dry-wet repeated environment containing H 2 S, when the Cr content exceeds 0.05 mass%, the general corrosion resistance and the pitting corrosion resistance remarkably decrease, and thus the Cr content is lower than 0.05 mass%.
  • Patent Literature 2 discloses a corrosion resistant steel for crude oil tanks that has excellent general corrosion resistance and local corrosion resistance and also can suppress generation of corroded products containing a solid S in which, to a steel containing C: 0.001 to 0.2 mass%, Si, Mn, P, and S are added in a proper amount and Cu: 0.01 to 1.5 mass%, Al: 0.001 to 0.3 mass%, and N: 0.001 to 0.01 mass% are added, and further at least one of Mo: 0.01 to 0.2 mass% or W: 0.01 to 0.5 mass% is added.
  • ballast tanks of crude oil tankers is under a very severe corrosion environment because the ballast tanks have a function of allowing safety navigation of vessels when there is no cargo and also, in the ballast tanks, seawater is poured therein. Therefore, for protecting corrosion of steel products for use in the ballast tanks, the formation of a protecting coating using an epoxy type paint and electrolytic protection are usually used in combination.
  • ballast tanks are subjected to severe corrosion due to the action of residual attached saline matter.
  • Patent Literature 3 discloses a corrosion-resistant low alloy steel for ballast tanks in which, to a steel containing C: 0.20 mass% or lower, Cu: 0.05 to 0.50 mass% and W: 0.01 to lower than 0.05 mass% are added as a corrosion-resistance improvement element, and further one or two or more of Ni, Ti, Zr, V, Nb, Ge, Sn, Pb, As, Sb, Bi, Te, and Be is/are added.
  • Patent Literature 4 discloses a corrosion-resistant low alloy steel for ballast tanks in which, to a steel products containing C: 0.20 mass% or lower, Cu: 0.05 to 0.50 mass% and W: 0.05 to 0.5 mass% are added as a corrosion-resistance improvement element, and further one or two or more of Ge, Sn, Pb, As, Sb, Bi, Te, and Be is/are added in a proportion of 0.01 to 0.2 mass%.
  • Patent Literature 5 discloses a corrosion-resistant low alloy steel for ballast tanks in which Cu: 0.05 to 0.15 mass% and W: 0.05 to 0.5 mass% are added to a steel containing C: 0.15 mass% or lower.
  • Patent Literature 6 discloses a ballast tank in which a protecting paint, such as a tar epoxy paint, a pure epoxy paint, a solventless epoxy paint, or a urethane paint, is applied to a low alloy corrosion-resistant steel product in which P: 0.03 to 0.10 mass%, Cu: 0.1 to 1.0 mass%, and Ni: 0.1 to 1.0 mass% are added as a corrosion-resistance improvement element to a steel containing C: 0.15 mass% or lower for resin coating the low alloy corrosion-resistant steel product.
  • This technique aims at extending the life of a protecting coating due to an improvement of corrosion resistance of the steel product itself to achieve maintenance-free over 20 to 30 years, during which vessels are used.
  • Patent Literature 7 proposes a steel product for ballast tanks aiming at achieving maintenance free of vessels by improving corrosion resistance by adding Cr: 0.2 to 5 mass% as a corrosion-resistance improvement element to a steel containing C: 0.15 mass% or lower.
  • Patent Literature 8 proposes a method for protecting ballast tanks from corrosion in which a steel product in which Cr: 0.2 to 5 mass% is added as a corrosion-resistance improvement element to a steel containing C: 0.15 mass% or lower is used as a constituent material and a ratio of the oxygen gas concentration in the ballast tank to the value in the atmosphere is adjusted to 0.5 or lower.
  • Patent Literature 9 proposes achieving maintenance-free of corrosion protection of vessels by improving corrosion resistance by adding Cr: 0.5 to 3.5 mass% to a steel containing C: 0.1 mass% or lower.
  • Patent Literature 10 discloses a steel product for vessels whose coating film damage resistance is improved by adding Ni: 0.1 to 4.0 mass% to a steel containing C: 0.001 to 0.025 mass% to thereby reduce maintenance expense, such as repair coating expense.
  • Patent Literature 11 discloses a steel for vessels having corrosion resistance in the environment of an exterior plate, ballast tanks, cargo oil tanks, and a cargo hold for ore and coal of vessels by adding Cu: 0.01 to 2.00 mass% and Mg: 0.0002 to 0.0150 mass% to a steel containing C: 0.01 to 0.25 mass%.
  • Patent Literature 12 or 13 discloses a steel product for cargo oil tanks whose resistance against general corrosion or local corrosion in a crude oil corrosion environment and a seawater corrosion environment by adding Cu: 0.05 to 2% and further compositely adding P, Ni, W, and Sn to a steel containing C: 0.01 to 0. 2% while suppressing the addition of Cr or Al.
  • Patent Literatures 12 and 13 aim at achieving both a crude oil corrosion environment and a seawater corrosion environment focusing on the fact that seawater is poured in the ballast tank disposed at the outside of a cargo oil tank when crude oil is not loaded. Then, with respect to the seawater corrosion environment, the corrosion resistance of the steel product itself is focused as corrosion resistance after a coating film of protecting coating of the external side of the cargo oil tank deteriorates. However, in the techniques, an improvement of the corrosion resistance in the state where a coating film is present is not considered at all.
  • corrosive gas such as H 2 S
  • the present inventors have repeated extensive examination for developing a corrosion-resistant steel product for tanker having excellent corrosion resistance in the corrosion environment of both oil tanks and ballast tanks of tankers. As a result, the present inventors have found that a corrosion-resistant steel product for tanker showing excellent corrosion resistance in a corrosion environment in oil tanks and ballast tanks of tankers is obtained by blending Cr: more than 0.1 mass% and 0.5 mass% or lower and Cu: 0.03 to 0.5 mass% and, as an alternative addition element, one or two or more elements selected from W: 0.01 to 0.5 mass%, Mo: 0.01 to 0.5 mass%, Sn: 0.001 to 0.2 mass%, Sb: 0.001 to 0.5 mass%, Ni: 0.005 to 0.3 mass%, and Co: 0.005 to 0.3 mass% and blending the components in such a manner as to satisfy a specific relationship. Then, the present invention has been accomplished.
  • the present invention provides a corrosion-resistant steel product for crude oil tanker as defined in claim 1.
  • Preferred embodiments are set out in the dependent claims.
  • the present invention can provide a steel product that is excellent in general corrosion resistance and local corrosion resistance in a corrosion environment of oil tanks of tankers in both a no-coating state or a state where zinc primer coating is performed or zinc primer coating and epoxy type coating are performed and also excellent in corrosion resistance after coating also in a corrosion environment of ballast tanks in a state where zinc primer coating is performed or zinc primer coating and epoxy type coating are performed. Accordingly, the steel product of the invention can be preferably used as materials constituting the oil tanks and the ballast tanks of tankers.
  • C is an element effective for increasing the strength of steel and 0.03 mass% or more of C needs to be added in order to secure a desired strength in the invention. In contrast, the addition exceeding 0.16 mass% reduces the weldability and the toughness of a welded heat affected zone. Therefore, C is added in the range of 0.03 to 0.16 mass%. C is in the range of preferably 0.05 to 0.15 mass% and more preferably 0.10 to 0.15 mass%.
  • Si is an element to be added as a deoxidizing agent and is also an element for increasing the strength of steel.
  • 0.05 mass% or more of Si is added in the invention.
  • Si is added in the range of 0.05 to 1.50 mass%.
  • Si is in the range of preferably 0.20 to 1.50 mass% and more preferably 0.30 to 1.20 mass%.
  • Mn is an element for increasing the strength of steel. In order to obtain a desired strength, 0.1 mass% or more of Mn is added in the invention. In contrast, the addition exceeding 2.0 mass% reduces the toughness and the weldability. Therefore, Mn is in the range of 0.1 to 2.0 mass%. Mn is added in the range of preferably 0.5 to 1.6 mass% and more preferably 0.7 to 1.5 mass%.
  • the P content is a harmful element that segregates in the grain boundary to reduce the toughness of steel, and thus the P content is preferably reduced as much as possible.
  • the toughness considerably decreases.
  • the corrosion resistance is also adversely affected. Therefore, the P content is in the range of 0.025 mass% or lower.
  • the P content is preferably 0.015 mass% or lower.
  • the P content is preferably 0.010 mass% or lower and more preferably 0.008 mass% or lower.
  • the upper limit of S is 0.01 mass%.
  • the upper limit is preferably 0.005 mass% or lower and more preferably 0.001 mass% or lower.
  • Al is an element to be added as a deoxidizing agent and needs to be added in a proportion of 0.005 mass% or more in the invention. However, the addition exceeding 0.10 mass% reduces the toughness of steel.
  • the upper limit of Al is 0.10 mass%.
  • the upper limit is preferably 0.01 to 0.06 mass% and more preferably 0.02 to 0.05 mass%.
  • N is a harmful element that reduces the toughness and thus the content thereof is reduced as much as possible.
  • the addition exceeding 0.008 mass% considerably reduces the toughness.
  • the upper limit is 0.008 mass%.
  • the upper limit is preferably 0.005 mass% or lower and more preferably 0.004 mass% or lower.
  • the corrosion resistance can be sharply improved compared with a steel product not containing Cr.
  • the above-described effect of Cr is not sufficiently obtained when the Cr content is 0.1 mass% or lower.
  • the addition exceeding 0.5 mass% reduces the toughness of a welding portion. Therefore, the Cr content is in the range of more than 0.1 mass% and 0.5 mass% or lower.
  • the Cr amount is preferably 0.11 to 0.20 mass% and more preferably 0.11 to 0.16 mass%.
  • Cu is an element for increasing the strength of steel, and is present in rust generated by corrosion of steel and has an effect of improving corrosion resistance. These effects are not sufficiently obtained when added in a proportion of lower than 0.03 mass%. In contrast, the addition exceeding 0.5 mass% has a possibility of causing a reduction in the toughness of a welded heat affected zone, surface cracking during manufacturing, etc. Therefore, Cu is added in the range of 0.03 to 0.5 mass%. Cu is preferably 0.04 to 0.20 mass% and more preferably 0.04 to 0.15 mass%.
  • the steel product of the invention needs to contain one or two or more elements selected from W, Mo, Sn, Sb, Ni, and Co as an alternative addition element in addition to the components described above.
  • W has an effect of suppressing pitting corrosion in the bottom plate of oil tanks of tankers and also has an effect of increasing the corrosion resistance against general corrosion of an upper deck of tankers or corrosion resistance after coating in a corrosion environment in which immersion in salt water and a high moistness state is repeated, such as in ballast tanks.
  • the above-described effect is developed by the addition of 0.01 mass% or more. However, the effect is saturated when the content exceeds 0.5 mass%.
  • W is added in the range of 0.01 to 0.5 mass%.
  • the content is preferably in the range of 0.02 to 0.3 mass%.
  • the content is more preferably in the range of 0.03 to 0.10 mass%.
  • W has the effect of improving the corrosion resistance as described above is considered to reside in that WO 4 2- generates in rust generated with corrosion of a steel plate, and the WO 4 2- suppresses the entry of chloride ion into the surface of the steel plate. It is also considered that FeWO 4 generate in a portion where the pH decreases, such as in an anode section on the surface of the steel plate, and the FeWO 4 also suppresses the entry of chloride ion into the surface of the steel plate, and as a result the corrosion of the steel plate is effectively suppressed. Furthermore, it is considered that the inhibiting action obtained by adsorption of WO 4 2- to the surface of a steel product suppresses the corrosion of the steel.
  • Mo has effects of not only suppressing the pitting corrosion in the bottom plate of oil tanks of tankers but increasing the corrosion resistance against general corrosion of an upper deck of tankers or the corrosion resistance after coating in a corrosion environment in which salt water immersion and a high moistness state are repeated, such as in ballast tanks.
  • the above-described effects are developed when Mo is added in a proportion of 0.01 mass% or more but the effects are saturated when added exceeding 0.5 mass%. Therefore, Mo is added in the range of 0.01 to 0.5 mass%.
  • the content is preferably in the range of 0.03 to 0.4 mass%.
  • the content is more preferably in the range of 0.03 to 0.10 mass%.
  • Mo has the effect of improving the corrosion resistance as described above is considered to reside in that MoO 4 2- generated in rust generated with the corrosion of a steel plate similarly as W, and the MoO 4 2- suppresses the entry of chloride ion into the surface of the steel plate, and as a result the corrosion of the steel plate is effectively suppressed.
  • Sn and Sb have effects of not only suppressing pitting corrosion in the bottom plate of oil tanks of tankers but increasing corrosion resistance against general corrosion of an upper deck of tankers or corrosion resistance after coating in a corrosion environment in which salt water immersion and a high moistness state are repeated, such as in ballast tanks.
  • the above-described effects are developed by adding Sn: 0.001 mass% or more and Sb: 0.001 mass% or more.
  • Sn is added in the range of 0.001 to 0.2 mass% and Sb is added in the range of 0.001 to 0.5 mass%.
  • Sn is preferably 0.005 to 0.10 mass% and more preferably 0.01 to 0.06 mass%.
  • Sb is preferably 0.02 to 0.15 mass% and more preferably 0.03 to 0.10 mass%.
  • Ni 0.005 to 0.3 mass%
  • Co 0.005 to 0.3 mass%
  • Ni and Co have an effect of improving the corrosion resistance in a no-coating state and the corrosion resistance in a state where an epoxy type coating is performed to a zinc primer coating film to no small extent. Therefore, these elements are preferably blended for further improving the corrosion resistance.
  • the above-described effect is developed by the addition of Ni: 0.005 mass% or more and Co: 0.005 mass% or more. In contrast, even when Ni: more than 0.3 mass% and Co: more than 0.3 mass% are added, the effect is saturated. Therefore, Ni and Co are preferably added in the above-described ranges.
  • Ni is preferably 0.01 to 0.2 mass% and more preferably 0.03 to 0.15 mass%.
  • Co is preferably 0.01 to 0.2 mass% and more preferably 0.03 to 0.15 mass%.
  • the element symbol of each equation represents the content (mass%) of each element.
  • Equation (1) above is an equation for evaluating the influence of each component exerted on the corrosion in oil tanks of tankers and the coefficient of the components for increasing the corrosion resistance is represented as minus and the coefficient of the components deteriorating the corrosion resistance is represented as plus. Therefore, steel products having a smaller X value are excellent in corrosion resistance.
  • the present inventors have investigated the relationship between the X value and the corrosion resistance of the steel products in a corrosion environment in oil tanks of tankers. As a result, the present inventors have found that when X is 0.5 or lower, the corrosion resistance in the corrosion environment in oil tanks of tankers is excellent but when X exceeds 0.5, the corrosion resistance is poor.
  • the steel products of the invention need to blend components so that the X value is 0.5 or lower.
  • the X value is more preferably 0.4 or lower.
  • Equation (2) above is an equation for evaluating the influence of each component exerted on the corrosion resistance after coating of ballast tanks.
  • the coefficient of the components for increasing the corrosion resistance is represented as minus and the coefficient of the components deteriorating the corrosion resistance is represented as plus. Therefore, steel products having a smaller Y value are excellent in corrosion resistance.
  • the present inventors have investigated the relationship between the Y value and the corrosion resistance after coating of the steel products in the corrosion environment in ballast tanks. As a result, the present inventors have found that when Y is 0.5 or lower, the corrosion resistance after coating in the corrosion environment in ballast tanks is excellent but when Y exceeds 0.5, the corrosion resistance is poor.
  • the steel products of the invention need to blend components so that the Y value is 0.5 or lower.
  • the Y value is more preferably 0.4 or lower.
  • the steel product of the invention preferably contains one or two or more elements selected particularly from W: 0.01 to 1.0 mass%, Mo: 0.01 to 0.5 mass%, Sn: 0.001 to 0.2 mass%, and Sb: 0.001 to 0.5 mass% among the above-described alternative addition elements, and secondly preferably contains one or two or more elements selected from Ni and Co.
  • the steel product of the invention can contain one or two or more elements selected from Nb, Ti, Zr, and V in the following ranges in addition to the above-described components in order to increase the strength of steel.
  • Nb 0.001 to 0.1 mass%
  • Ti 0.001 to 0.1 mass%
  • Zr 0.001 to 0.1 mass%
  • V 0.002 to 0.2 mass%
  • Nb, Ti, Zr, and V each are elements having an effect of increasing the strength of steel products, and can be selected and added according to a required strength.
  • Nb, Ti, and Zr be added in a proportion of 0.001 mass% or more and V be added in a proportion of 0.002 mass% or more.
  • Nb, Ti, and Zr are added in a proportion of more than 0.1 mass% and V is added in a proportion of more than 0.2 mass%, the toughness decreases.
  • Nb, Ti, Zr, add V are preferably added in the above-described ranges.
  • Nb is preferably 0.004 to 0.05 mass% and more preferably 0.005 to 0.02 mass%.
  • Ti is preferably 0.002 to 0.03 mass% and more preferably 0.002 to 0.01 mass%.
  • Zr is preferably 0.001 to 0.05 mass% and more preferably 0.002 to 0.01 mass%.
  • V is preferably 0.003 to 0.15 mass% and more preferably 0.004 to 0.1 mass%.
  • the steel product of the invention can contain one or two or more elements selected from Ca, REM, and Y in the following ranges in addition to the above-described components.
  • Ca, REM, and Y each have an effect of improving the toughness of a welded heat affected zone, and can be added as required.
  • the above-described effects are obtained by adding Ca: 0.0002 mass% or more, REM: 0.0002 mass% or more, and Y: 0.0001 mass% or more.
  • Ca: more than 0.01 mass%, REM: more than 0.015 mass%, and Y: more than 0.1 mass% are added, the toughness decreases on the contrary.
  • Ca, REM, and Y are preferably in the above-described ranges.
  • Ca is preferably 0.001 to 0.005 mass% and more preferably 0.001 to 0.003 mass%.
  • REM is preferably 0.0005 to 0.015 mass% and more preferably 0.001 to 0.010 mass%.
  • Y is preferably 0.0001 to 0.05 mass% and more preferably 0.0002 to 0.01 mass%.
  • the steel product of the invention can further contain B in the following range in addition to the above-described components.
  • B is an element for increasing the strength of the steel products and can be added as required. In order to obtain the above-described effect, 0.0002 mass% or more of B is preferably added. However, B is added exceeding 0.003 mass%, the toughness decreases. Therefore, B is preferably added in the range of 0.0002 to 0.003 mass%. B is preferably 0.0002 to 0.002 mass% and more preferably 0.0002 to 0.0015 mass%.
  • the steel product for tankers of the invention manufactured by the above-described method using a steel base material having the above-described component composition has a feature in that the steel product for tankers of the invention is excellent not only in the corrosion resistance (general corrosion resistance, local corrosion resistance) in no-coating state but in the corrosion resistance after coating.
  • the steel product for crude oil tanks of the invention can sharply improve the local corrosion resistance and general corrosion resistance by forming a zinc primer coating film while adjusting the coating amount of a coating, such as a primer containing a metal Zn or a Zn compound (hereinafter collectively referred to as a "zinc primer”) to 1.0 g/m 2 or more in terms of Zn content.
  • the coating amount is preferably 10 g/m 2 or more in terms of average Zn content.
  • the coating amount is more preferably 15 g/m 2 or more.
  • the relationship between the coating film thickness of the zinc primer and the Zn content of the surface of the steel product depends on the Zn content in the zinc primer. In general, when the thickness is 10 ⁇ m or more in terms of average coating thickness, the entire surface of the steel product can be covered. Irrespective of the kind of the zinc primer, the coating amount of at least 1.0 g/m 2 or more can be secured. From the viewpoint of increasing the corrosion resistance, the upper limit of the film thickness of the zinc primer is not particularly determined. However, when the coating film becomes thick, the cutting properties or weldability decreases.
  • the film thickness of the zinc primer is preferably 100 ⁇ m or lower and more preferably 50 ⁇ m or lower.
  • Such zinc primer coating may be performed, for example, after performing shotblasting treatment to the surface of the steel product.
  • the steel product for crude oil tanks of the invention can form an epoxy type coating film by applying an epoxy type paint or the like on a no-coating steel product surface or a steel product surface after the application of the zinc primer.
  • the local corrosion resistance and general corrosion resistance can be further improved as compared with the case of former steel products for vessels and also, particularly when used for ballast tanks or the like under a severe corrosion environment due to seawater, an effect of improving a more preferable corrosion resistance after coating, for example, coating film swelling resistance, is obtained.
  • the epoxy type coating film is not particularly limited, and various kinds of epoxy type resin can be used.
  • a modified epoxy resin, a tar epoxy resin, and the like can be used.
  • the film thickness of the epoxy type coating film is not particularly limited, and is preferably 500 ⁇ m or lower and more preferably 350 ⁇ m or lower from the viewpoint of coating cost or workability and can be selected as appropriate according to required properties.
  • a corrosion coupon 1 placed on the upper back side of the test chamber was repeatedly subjected to temperature changes for 180 days in one cycle of 30°C ⁇ 4 hours + 50°C ⁇ 4 hours through the temperature-controlled plate 3 containing a heater and a cooling system to generate dew condensation water on the surface of the coupon 1, thereby causing general corrosion.
  • the reference numeral 5 represents emission gas from the test chamber.
  • the corrosion test equipment is double-type equipment containing a corrosion test chamber 8 and a constant-temperature bath 9.
  • a test liquid 12 capable of causing the same local corrosion as that generating in the bottom plate of an actual oil tank was put, and a coupon 7 was immersed therein.
  • Used as the test liquid 12 was a liquid containing artificial seawater specified in ASTM D1141 as a test mother water, into which a mixed gas (introduced gas 10) in which the partial pressure ratio was adjusted to 5 vol% O 2 + 10 vol% H 2 S and which contained the balance N 2 gas was introduced.
  • the temperature of the test liquid 12 was held at 50°C by adjusting the temperature of the water 13 put into the constant-temperature bath 9. Since the introduced gas 10 was continuously supplied, the test liquid 12 was always stirred.
  • the reference numeral 11 represents emission gas from the test chamber.
  • each coupon was subjected to a corrosion test in which one cycle of (held in artificial seawater having a temperature of 30°C for 1 day) ⁇ (held in a wet atmosphere having a relative humidity of 98 to 99% at a temperature of 40°C for 1 day) was repeated by 60 cycles (for 120 days) as a corrosion cycle test in which the environment of a ballast tank of an actual ship was simulated.
  • the corrosion resistance of each coupon was evaluated as follows. The coupons having a coating film in the conditions A and B were measured for the coating film swelled area generated around the scratch.
  • the corrosion resistance test results of (1) to (3) were shown in Table 2 with the X values and the Y values determined from the component composition of each steel plate.
  • Table 2 shows that the thick steel plates of No. 1 to No. 30 satisfying the component composition of the invention and the conditions of the X value and the Y value exhibit excellent corrosion resistance higher than a target level as a ratio to a base steel product (No. 36) in all the corrosion tests of (1) to (3) and, in contrast, corrosion exceeding a target level as a ratio to the steel product of No. 36 is observed in the thick steel plates of No. 31 to No. 35 not satisfying the conditions of the invention in any one or more of the corrosion tests.
  • the steel product of the present invention can be preferably used not only in crude oil tankers but also crude oil tanks of other vessels and crude oil tanks used on the ground, for example.

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Claims (5)

  1. Produit en acier résistant à la corrosion pour pétrolier de brut, constitué de :
    C : 0,03 à 0,16 % en masse, Si : 0,05 à 1,50 % en masse, Mn : 0,1 à 2,0 % en masse, P : 0,025 % en masse ou moins, S : 0,01 % en masse ou moins, Al : 0,005 à 0,10 % en masse, N : 0,008 % en masse ou moins, Cr : plus de 0,1 % en masse et 0,5 % en masse ou moins et Cu : 0,03 à 0,5 % en masse et, en tant qu'élément d'addition alternatif, un ou deux éléments ou plus choisis parmi W : 0,01 à 0,5 % en masse, Mo : 0,01 à 0,5 % en masse, Sn : 0,001 à 0,2 % en masse, Sb : 0,001 à 0,5 % en masse, Ni : 0,005 à 0,3 % en masse et Co : 0,005 à 0,3 % en masse et, éventuellement, également constitué d'un ou deux éléments ou plus choisis parmi Nb : 0,001 à 0,1 % en masse, Ti : 0,001 à 0,1 % en masse, Zr : 0,001 à 0,1 % en masse et V : 0,002 à 0,2 % en masse en plus de la composition en constituants, un ou deux éléments ou plus choisis parmi Ca : 0,0002 à 0,01 % en masse, terres rares : 0,0002 à 0,015 % en masse et Y : 0,0001 à 0,1 % en masse en plus de la composition en constituants, et/ou B : 0,0002 à 0,003 % en masse en plus de la composition en constituants, de sorte que les constituants satisfassent à ce que la valeur X définie par l'équation (1) soit inférieure ou égale à 0,5 et à ce que la valeur Y définie par l'équation (2) soit inférieure ou égale à 0,5 ; Valeur X = 1 − 0,8 × Cu 0,5 × 1 − 0,8 × W + 0,4 × Mo 0,3 × 1 − 0,8 × Sn + 0,8 × Sb 0,5 × 1 − 0,05 × Cr + 0,03 × Ni + 0,03 × Co 0,3 × 1 + S / 0,01 + P / 0,05
    Figure imgb0010
     et Valeur Y = 1 − 0,3 x Cr 0,3 x 1 − 0,8 x W + 0,5 x Mo 0,3 x 1 − Sn + 0,4 x Sb 0,3 x 1 − 0,1 x Ni + 0,1 x Co + 0,05 x Cu 0,3 x 1 + S / 0,01 + P / 0,08 0,3 }
    Figure imgb0011
     et
    le reste contenant du Fe et des impuretés inévitables et
    le symbole d'élément dans chaque équation représentant la teneur (% en masse) de chaque élément.
  2. Produit en acier résistant à la corrosion pour pétrolier de brut selon la revendication 1, comprenant un ou deux éléments ou plus choisis parmi W : 0,01 à 0,5 % en masse, Mo : 0,01 à 0,5 % en masse, Sn : 0,001 à 0,2 % en masse et Sb : 0,001 à 0,5 % en masse en tant qu'élément d'addition alternatif.
  3. Produit en acier résistant à la corrosion pour pétrolier de brut selon la revendication 2, comprenant en outre un ou deux éléments choisis parmi Ni : 0,005 à 0,3 % en masse et Co : 0,005 à 0,3 % en masse en plus des éléments d'addition alternatifs.
  4. Produit en acier résistant à la corrosion pour pétrolier de brut selon l'une quelconque des revendications 1 à 3, qui est obtenu par formation d'un film de revêtement d'apprêt contenant du Zn sur la surface du produit en acier.
  5. Produit en acier résistant à la corrosion pour pétrolier de brut selon l'une quelconque des revendications 1 à 4, qui est obtenu par formation d'un film de revêtement de type époxy sur la surface du produit en acier.
EP09835097.8A 2008-12-24 2009-12-22 Matériau en acier résistant à la corrosion pour pétrolier de brut Active EP2377963B1 (fr)

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TWI404807B (zh) 2013-08-11
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